Method of manufacturing rubberlike materials



Patented Oct. 26, 1943 UNITED STATES PATENT OFFICE METHOD OFMANUFACTURING RUBBER- I LIKE MATERIALS Tadao Okita, Imazucho,Nishinomiya, Japan; vested in the Alien Property Custodian No Drawing.Application November 29, 1939, Serial No. 306,684

11 Claims. (01. 260-79) The present application is a continuation in(VI) ametallic compound of a monothio-diglycol part of my priorcopending application Serial No. O'HhAM, 94,196, filed August 4, 1936,for "Method oi manufacturing oil-proof rubberlike materials."

The present invention relates to a method of CmHl-VAMB manufacturingoil-proof rubber-like materials by (v11) metallic compound of a glycolthe reaction of a dihalogen compound of an olefin c H'JMB such asethylene or of an ether, a halogen compound of a thio-glycol, or amixture of the said substances, upon a metallic compound of a thio- 0 ora mixture of the said substances. In the above diglycol, a metalliccompound of glycol, or a mixchemical expressions, A is an oxygen groupeleture of the said substances under ordinary teniment such as O, S, Se,Te; X is a halogen group perature or heating. v element such as Cl, F,I, Br; Me is a metal of The present invention has for its object an easythe group Na, K, Mg, Ag, Zn, Ca; 112, n, m, 'n'. manufacture ofrubber-like materials of great y, z are positive integers; m, 122' beingbetween 1 oil-proof property and elasticity and of the least and 2; n, nbeing between 1 and 4; y, 2 bein oflensive odor. between 2 and 4.

Research has heretofore been carried out with To take a few examples,

a view to improving the quality of rubber which, (1) The mixture byrespective chemical equivain spite of its extensive utility, is of verylimited lents of (V) di-sulphide of sodium ethylate ofl-proof propertyand also with a view to devel- 0.11pm

oping rubber substitutes 01' great oil-proof property. Such research hasresulted in the manufaeture of materials which are not only of asClHAONB great elasticity as rubber but of great oil-proof (which is akind of metallic compound of a polyn ope bu t e materials have thedisadvanthio-diglycol) and (I) ethylene chloride Cal-I401: tages ofrequiring intricate manufactur ng methis in reaction by heating at C 150Q ods and of possessing offensive odors. so th for about two hours. Theethereal reaction h known Pmcesses are $15111 unsatlsfacml'y therebycaused separates sodium chloride, leaving practical a rubber-likematerial.

The present invention is the method of manu- (2) The mixture byrespective chemical equivfflc urln l-pr f rubber-like materials by thealents of (V) a magnesium compound of tetraspecial reaction. underordinary temperature or t io-di-thio-glycol heating, of (I) a dihalogencompound of an ole- H S fln Cal-hex: (e. g. of ethylene), (H) adihalogen compound of an ether 8 0.11): cams 0 (which is a kind ofmetallic compound of a thicdiglycol) and (n) a bromine compound of 40methyl-ethyl ether (III) a halogen compound at a polythio-diglycolO-Hr-x I /O HiBr 82 0 l'Hla'x cflBr I (IV) ahalogen compound ofamonothio-diglycol is put in reaction by heating at c 0.1m: The etherealreaction thereby caused separates magnesium bromide, leaving arubber-like mate- I e) The mixture by chemieal equivalents or or amixture of the said substances upon (V) a (VII) potassium glycolatemetallic compound of a polythiodiglycol O-HQDAMO s11 cmox C- HwAMQ(which is a kind of metallic compound of glycol).

elevated temperatures up to about 150 C.

and (III) trisulphide of ethyl iodide and propyl iodide CgHJ CiHtI isput in reaction by; heating at 70 C.-l5() C. The ethereal reactionthereby caused separates potassium iodide, leaving rubber-likematerials.- In any case, however, if (I), (II) or (IV) i. e. a dihalogencompound of an olefin or of an ether or a halogen compound of amonothio-diglycol whose chemical expression is acts upon (VI) a metalliccompound of a. mono thio-diglycol whose chemical expression is C mHBmAMBor if (VII) a metallic compound of a glycol acts upon (IV) a halogencompound of a monothio= diglycol; or if (I) or (E) i. e, a dihalogencom= pound of an olefin or a dihalogen compound of an ether acts upon(VII) a metalliccompound of a glycol, not rubber-like materials but apowder is engendered.

It will be clear, therefore, that in reacting (I) (11), (III), (IV) ormixtures thereoi with (V), (VI), (VII) or mixtures thereof one shouldselect these compounds or mixtures thereof so as to avoid the abovedescribed inoperative combinations (I)+(VI), (H)+(VI), (IV)+(VI), (I)+(VII), (II)+(VII), (IV)+(VII), and so as to give substantially only thefollowing combinations: (I) +(V), (II) +(V), (In) +(V), (IV) (V),(HI)+(VI), (III)+(VII).

Although tests have been conducted on a very large number of reactionstypically representative of the various classes of reaction abovedefined, and although such tests have indicated that nearly all thereactions above defined are effective to produce new and usefulcompositions most of which have properties resembling those of more orless vulcanized rubber, nevertheless, I believe that the most widelyuseful new compositions of my invention are those obtained by choosingm, m, n, n, 1;, a, A, Me as follows: m, m are between 1 and 2 (beingpreferably 2); n, is between 2 and 4: n is between 2 and 4; 3 is between2 and 4; z is between 2 and 4; A=oxygen or sulphur; Me=sodium. potassiumor magnesium. (Whenever an integer is defined as be ing between twolimiting numbersfthe range of values of such integer'is'to be taken toinclude both limiting numbers.)

In particular I prefer as the very best ndi ides of practising myinvention the nine reactions resulting from the combining of (I) (V)where A=oxygen, X=chlorine, m=2, m'=2, n=2, 8 or 4, and 11:2, 3 or 4.These nine embodiments may all be defined as the reactions 01adihalogenated olefin CnHzaCl: (where n=2,- 3 or 4) with a polysulphideof sodium ethylate c on an a "k carom (where 11=2, 3 0r 4). Thereactions may be effected at ordinary temperatures on at moderate Thesenine reactions may be schematically represented as follows:

omornoNa +cuncn CHaCHsONa CH:CH ONa +CsH|C 2 CHaCHgONB CHQCHQON +cuncsongcnaom omomons S5 +CaHcC1s omissions CHsCHQONa +C3HaCla omomomCHzCHgONB s. +csntcuomcngom CHaCEaONa Sz +CH5C1i3 \CHQCHBONB CEiCHsONhBa +CtHaC1a CHaCHsONa CHzCHgONa +C4Idalx illustration, it will beunderstood generally that v has the formula CHECHZONB omcmom andmaintaining the mixture at a temperature between about C. and C. untilsodium chloride and a rubber-like material are formed.

2. The method of manufacturing an oil-proof rubber-like material, whichcomprises mixin propylene chloride which has the formula. CaHcCla withthe trisuiphide of sodium ethylate which has the formula OHaCHaONaCHlOHaONo and maintaining the mixture at a temperature between about 70C. and 150 C. until sodium chloride and a rubber-like material areformed.

3. The method of manufacturing an oil-proof -45 rubber-like material,which comprises mixing butylene chloride which has the formula CiHaClzwith the'disulphide of sodium ethylate which has the formula CHaCHzONBSz\ CHzCHrONa and maintaining the mixture at a temperature between about70 C. and 150 C. until sodium chloride and a rubber-like material areformed.

4. The method of manufacturing oil-proof rubher-like material by mixinga metallic compound of polythio-glycol which has the formula C2H4AMwhere y is an integer between 2 and 4,'Me is a metal of the groupconsisting of Na, K, .Mg, Zn, Ag, Ca, and A is an element of the groupconsisting of oxygen and sulphur, with a dihalogenated olefin having theformula C2H4X2, where X is a halogen, and maintaining said mixture at areactive temperature.

5. The method of manufacturing oil-proof rubber-like material by mixinga metallic compound of polythio-glycol which has the formula \C2H4AM8where y is an integer between 2 and-4, Me is a metal ofthe groupconsisting of Na, K, Mg, Zn, Ag, Ca, and A is an element of the groupconsisting of ox gen and sulphur, with a dihalogenfin having the formulacnI'IZnXZ, where n is an integer between 2 and 4 and X is a halogen, and

maintaining said mixture at a reactive temperaated olefin having theformula Cal-16x2, where X r is a halogen, and maintaining said mixtureat a reactive temperature.

6. The method of manufacturing oil-proof rubber-like material by mixinga metallic compound of polythio-glycol which has the formula CzHiAMc rCzHrAMe where y is an integer between 2 and 4, Me is a metal of thegroup consisting of Na, K, Mg, Zn, Ag, Ca, and A is an element of thegroup consisting of oxygen and sulphur, with a dihalogenated olefinhaving the formula C-iHsXz, where X is a halogen, and maintaining saidmixture at a reactive temperature.

7. The method of manufacturing oil-proof rubher-like material by mixinga metallic compound of polythio-glycol which has [7238 formula where Meis a metal of the groupconsisting of Na, K, Mg, Zn, Ag, Ca, with adihalogenated oleber=like material by mixing a metallic compound ofpolythio-glycol which has the formula ciHioMe ozrnoMe where Me is ametal of the group consisting of Na, K, Mg, Zn, Ag, Ca, with adihalogenated' olefin having the formula CnHZnXz, where n is an integerbetween 2 and 4 and X is a halogen, and maintaining said mixture at areactive temperature.

10. The method of manufacturing oil-proof rubber-like material by mixinga metallic compound of polythio-glycol which has the formula where 1/ isan integer between 2 and', Me is a metal of the group consisting of Na,K, Mg, Zn, Ag, Ca, and A is an element of the group consisting of oxygenand sulphur, with a dihalogenated olefin having the formula CnHznXe,where n is an integer between 2 and 4 and X is a halogen, andmaintaining said mixture at a reactive temperature.

11. The method of manufacturing oil-proof rubber-like material by mixinga metallic compound of polythio-glycol which has the formula C HzmAMcwhere m and m are integers between 1 and 2, y is an integer between 2and 4, Me is a metal of the group consisting of Na, K, Mg, Zn, Ag, Ca,and A is an element of the group consisting of oxygen and sulphur, witha dihalogenated olefin having the formula CnH2nX2, where n is an integerbetween 1 and 4 and X is a halogen, and maintaining said mixture at areactive temperature,

T. OKITA.

